(Graph Presented). In this study, we report the synthesis of Ti-doped mesoporous hematite films by soft-templating for application as photoanodes in the photoelectrolysis of water (water splitting ... [more ▼]

(Graph Presented). In this study, we report the synthesis of Ti-doped mesoporous hematite films by soft-templating for application as photoanodes in the photoelectrolysis of water (water splitting). Because the activation of the dopant requires a heat treatment at high temperature (≥800°C), it usually results in the collapse of the mesostructure. We have overcome this obstacle by using a temporary SiO2 scaffold to hinder crystallite growth and thereby maintain the mesoporosity. The beneficial effect of the activated dopant has been confirmed by comparing the photocurrent of doped and undoped films treated at different temperatures. The role of the mesostructure was investigated by comparing dense, collapsed, and mesoporous films heated at different temperatures and characterized under front and back illumination. It turns out that the preservation of the mesotructure enables a better penetration of the electrolyte into the film and therefore reduces the distance that the photogenerated holes have to travel to reach the electrolyte. As a result, we found that mesoporous films with dopant activation at 850°C perform better than comparable dense and collapsed films. [less ▲]

Polymeric sol–gel route has been used for the preparation of TiO2 and RE2O3–TiO2 (RE = Eu, Er) mesoporous thin films by evaporation induced self-assembly method using Si (100) as a substrate. The ... [more ▼]

Polymeric sol–gel route has been used for the preparation of TiO2 and RE2O3–TiO2 (RE = Eu, Er) mesoporous thin films by evaporation induced self-assembly method using Si (100) as a substrate. The influence of the relative humidity (RH) on the preparation of the film has been studied being necessary to work under 40% RH in order to obtain homogeneous and transparent thin films. The films were annealed at different temperatures until 900 °C/1 h and the anatase crystallization and its crystal size evolution were followed by low angle X-ray diffraction. Neither the anatase–rutile transition nor the formation of other compounds was observed in the studied temperature range. Ellipsoporosimetry studies demonstrated that the thickness of the thin films did not change after calcination at 500 °C, the porosity was constant until 700 °C, the pore size increased and the specific surface area decreased with temperature. Moreover, the effect of the doping with Er3 + and Eu3 + was studied and a clear inhibition of the crystal growth and the sintering process was detected (by transmission electron and atomic force microscopy) when the doped films are compared with the undoped ones. Finally, Eu3 + and Er3 + f–f transitions were detected by PL measurements. [less ▲]

The intercalation and de-intercalation of lithium cations in electrochromic tungsten oxide thin films are significantly influenced by their structural and surface characteristics. In this study, we ... [more ▼]

The intercalation and de-intercalation of lithium cations in electrochromic tungsten oxide thin films are significantly influenced by their structural and surface characteristics. In this study, we prepared two types of amorphous films via the sol-gel technique: one dense and one mesoporous in order to compare their response upon lithium intercalation and de-intercalation. According to chronoamperometric measurements, Li+ intercalates/de-intercalates faster in the mesoporous film (24s/6s) than in the dense film (48s/10s). The electrochemical measurements (cyclic voltammetry and chronoamperometry) also showed worse reversibility for the dense film compared to the mesoporous film, giving rise to important Li+ trapping and remaining coloration of the film. Raman analysis showed that the mesoporous film provides more accessible and various W-O surface bonds for Li+ intercalation. On the contrary, in the first electrochemical insertion and de-insertion in the dense film, Li+ selectively reacts with a few surface W-O bonds and preferentially intercalates into pre-existing crystallites to form stable irreversible LixWO3 bronze. [less ▲]

A key issue in the commercialization of dye-sensitized solar cells is to maintain high efficiency and long lifetime. As reported in the literature, dye-sensitized solar cells are stable under visible ... [more ▼]

A key issue in the commercialization of dye-sensitized solar cells is to maintain high efficiency and long lifetime. As reported in the literature, dye-sensitized solar cells are stable under visible light soaking but thermal stress and UV exposure lead to efficiency degradation. However, all the stability studies published so far have been performed on cells whose TiO2 electrodes were prepared by tape casting or screen printing of nanoparticle pastes/inks. The present study concerns cells based on highly porous templated TiO2 electrodes, whose larger surface area could enhance the negative effects of thermal stress, light soaking and UV exposure. The long-term stability of these cells is compared with a classical nanoparticle-based cell using current-voltage measurements (I-V curves) and electrochemical impedance spectroscopy. Due to their higher active interface, templated cells are more sensitive than nanoparticle cells to UV illumination, although this can be easily solved in both cases by the use of a UV filter. The templated cells are as stable as the nanoparticle cells under visible light soaking (UV filtered). However, we showed that templated cells are more stable under thermal stress. Moreover, as evidenced by electrochemical impedance spectroscopy, templated cells show lower transfer resistance, as well as lower recombination resistance compared to nanoparticle cells. The crystallite connectivity promoted by the templating route seems to favor the electron transfers inside the porous layer. Using templated films in dye-sensitized solar cells is therefore really promising because higher conversion efficiencies are reached without promoting cell degradation. [less ▲]

Liquid-state dye-sensitized solar cells can suffer from electrolyte evaporation and leakage. Therefore solid-state hole transporting materials are investigated as alternative electrolyte materials. However, in solid-state dye-sensitized solar cells, optimal TiO2 films thickness is limited to a few microns allowing the adsorption of only a low quantity of photoactive dye and thus leading to poor light harvesting and low conversion efficiency. In order to overcome this limitation, high surface area templated films are investigated as alternative to nanocrystalline films prepared by doctor-blade or screen-printing. Moreover, templating is expected to improve the pore accessibility what would promote the solid electrolyte penetration inside the porous network, making possible efficient charge transfers. In this study, films prepared from different structuring agents are discussed in terms of microstructural properties (porosity, crystallinity) as well as impact on the dye loading and Spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) solid electrolyte filling. We first report Rutherford backscattering spectrometry as an innovative non-destructive tool to characterize the hole transporting materials infiltration. Templated films show dye loading more than two times higher than nanocrystalline films prepared by doctor-blade or screen-printing and solid electrolyte infiltration up to 88%. [less ▲]

Liquid-state dye-sensitized solar cells can suffer from electrolyte evaporation and leakage. Therefore solid-state hole transporting materials are investigated as alternative electrolyte materials. However, in solid-state dye-sensitized solar cells, optimal TiO2 films thickness is limited to a few microns allowing the adsorption of only a low quantity of photoactive dye and thus leading to poor light harvesting and low conversion efficiency. In order to overcome this limitation, high surface area templated films are investigated as alternative to nanocrystalline films prepared by doctor-blade or screen-printing. Moreover, templating is expected to improve the pore accessibility what would promote the solid electrolyte penetration inside the porous network, making possible efficient charge transfers. In this study, films prepared from different structuring agents are discussed in terms of microstructural properties (porosity, crystallinity) as well as effect on the dye loading and Spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) solid electrolyte filling. Different techniques such as transmission electron microscopy (TEM), atmospheric poroellipsometry (AEP) and UV-visible absorption spectroscopy (UV-vis.) have been used to describe the microstructural features of the films. Besides, we have implemented Rutherford backscattering spectrometry (RBS) as an innovative non-destructive tool to characterize the hole transporting materials infiltration. Templated films show dye loading more than two times higher than nanocrystalline films prepared by doctor-blade or screen-printing and solid electrolyte infiltration up to 88%. [less ▲]

DSSCs have been reported by O’Regan and Grätzel in the early nineties as a very promising alternative to conventional photovoltaic silicon devices. Main benefits of these cells are their low cost as well ... [more ▼]

DSSCs have been reported by O’Regan and Grätzel in the early nineties as a very promising alternative to conventional photovoltaic silicon devices. Main benefits of these cells are their low cost as well as their mild manufacturing process. In most of the specific literature, DSSCs are made of TiO2 films prepared by doctor-blade or screen-printing of anatase nanoparticles paste. However, due to the random organization of the nanoparticles, pore accessibility by the dye and electrolyte could be incomplete. Moreover, some anatase crystallites could suffer from a lack of connectivity, leading to electron transfer issues. The strategy adopted by our group to improve photovoltaic efficiencies involves a templating-assisted process allowing the preparation of highly porous layers with well-ordered and accessible pores as well as improved crystallites connectivity. The main goal is to increase the film surface area and to perfectly control the mesostructure in order to maximize the adsorption of active dye and the electrolyte infiltration inside the porous network. This talk especially focuses on the templating-assisted synthesis of TiO2 and ZnO semiconducting layers used as photoelectrode in DSSCs. Besides, due to the surface area improvement as well as the perfect control of the pore organization and the pore size, the templating strategy can be an effective solution to overcome light harvesting and solid electrolyte filling limitations encountered in solid-state DSSCs. Special effort is paid to the tuning of the TiO2 and ZnO semiconducting layers mesostructure in order to match with solid-state DSSC applications. [less ▲]

The efficiencies of dye sensitized solar cells (DSCs) are boosted up to 12% by NIR light harvesting dyes and with the usage of scattering layer in the device preparation.The importance of Titania ... [more ▼]

The efficiencies of dye sensitized solar cells (DSCs) are boosted up to 12% by NIR light harvesting dyes and with the usage of scattering layer in the device preparation.The importance of Titania scattering layers was studied as a part of this work. These scattering layers were prepared from two different grain-sizes (100 nm & 500 nm) for SQ2-NIR and N3-UV/Vis DSCs. The 100 nm grain-sized Titania paste was commercially supplied and 500 nm grain-sized Titania paste was prepared according to literature. The morphological and structural properties of these bigger grain-sized Titania layers were deliberated by using and Scanning Electron Microscope (SEM) and X-Ray diffraction (XRD) measurements. The influence of these bigger grain-sized Titania scattering layers in SQ2-NIR and N3-UV/Vis DSCs were expounded by using various electro-optical characterization techniques such as light I-V, electrochemical impedance spectroscopy (EIS) shown in Figure 1 and external quantum efficiency (EQE) measurements. The importance of understanding the influence of these bigger grain-sized scattering Titania layers could pave a way for future design and optimizing of DSCs for increasing the amount of light harvesting. [less ▲]

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes ... [more ▼]

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes with a thickness of 10-15 µm. However, in solid-state DSSCs, TiO2 films thickness is limited to few µm allowing the adsorption of only a low quantity of photoactive dye and thus leading to a poor light harvesting and low conversion efficiencies. In order to overcome this limitation, templated-assisted dip-coating techniques are used to obtain thin films with high surface area. Moreover, templating is expected to improve the pore accessibility what would promote the solid electrolyte penetration inside the porous network, making possible efficient charge transfers. In this study, films prepared from different structuring agents are discussed in terms of microstructure properties (porosity, crystallinity) and impact on the dye loading and solid electrolyte filling. As-obtained templated films have been compared to nanocrystalline films prepared by doctor blade or screen printing as reference. Different techniques such as transmission electron microscopy (TEM), atmospheric poroellipsometry (AEP) and UV-visible absorption spectroscopy (UV-vis.) have been used to describe the microstructural features of the films. Solid electrolyte infiltration has been extensively investigated by Rutherford Backscattering Spectroscopy (RBS). Finally, templated films were evaluated as photoelectrode in solid-state DSSCs and compared to nanoparticles layers. [less ▲]

The present thesis is dedicated to the synthesis and characterization of the TiO2 semiconductor layer used as photoelectrode in dye-sensitized solar cells (DSSCs), with the aim to improve their ... [more ▼]

The present thesis is dedicated to the synthesis and characterization of the TiO2 semiconductor layer used as photoelectrode in dye-sensitized solar cells (DSSCs), with the aim to improve their photovoltaic efficiencies. DSSCs have been reported by O’Regan and Grätzel in the early nineties as a very promising alternative to conventional silicon devices. Main benefits of these cells are their low cost and their mild manufacturing process. In most of the specific literature, DSSCs are made of TiO2 films prepared by doctor-blade or screen-printing of anatase nanoparticles paste. However due to the random organization of the nanoparticles, pore accessibility by the dye and electrolyte could be incomplete and some anatase crystallites could be not connected impeding electron transfer. The strategy adopted to improve the films properties and thus PV efficiencies involves a surfactant-assisted process allowing the preparation of highly porous layers with well-ordered and accessibles pores as well as improved crystallites connectivity. The main goal of this work is to increase the film surface area and perfectly control the mesostructure in terms of thickness, pore size, pore organization and pore accessibility in order to maximize the adsorption of active dye and the electrolyte infiltration inside the porous network. Special attention was paid to the tuning of the experimental settings such as the relative humidity conditions, the withdrawal speed and the choices of substrate and surfactant. Moreover, for DSSCs applications, TiO2 film has to be crystallized in form of anatase. Perfect balance between high crystallinity and mesostructure preservation was studied in order to enhance the cells efficiencies. Besides, templated films challenge is to obtain thick layers. Indeed, monolayer films are only a few hundred nanometers thick. To increase the film thickness and thus the quantity of active material, a multilayer process was tuned. Special effort was paid to overcome the surface area limitation induced by the repeated thermal treatments applied during multilayer process. We propose an alternative thermal treatment in order to limit the mesostructure degradation. We also define the maximum crystal size compatible with the preservation of the mesoarchitecture initially induced by templating. Thick films up to 4 µm were prepared from this multilayer process and show excellent efficiency in combination with N-719 dye (6.1%) when compared to values reported in the literature. Such mesostructured templated films were compared in terms of photovoltaic performances with TiO2 nanoparticles films, generally used in DSSCs. In a second part, as the goal of this thesis is to improve the current nanoparticles-based DSSCs and prove the viability of the templating alternative, a comparison of the long-term stability of both technologies was performed. To our knowledge, long-term stability of templated DSSCs has never been reported at this time. However, in case of templated films, the surface area is highly improved and the negative effects of thermal stress, light soaking and UV exposure could be heightened. Due to their higher active interface, templated films are more sensitive than nanoparticles samples to UV illumination, what can be easily solved by the use of a UV filter. However, they are as stable as nanoparticles samples under visible light soaking (UV filtered) and under thermal stress. In addition, cells were characterized by electrochemical impedance spectroscopy (EIS). Templated cells show lower transfer resistance, as well as longer electron lifetime compared to nanoparticles DSSCs. Using templated films in DSSCs is therefore really promising because higher conversion efficiencies are reached without any increase in cells degradation. Finally, stability limitation encountered by DSSCs are mostly related to the use of liquid electrolytes, which can leak out the cell. Solid-state hole transporting materials are investigated in order to overcome this issue. However, in solid-state DSSCs, TiO2 films thickness is limited to a few microns allowing the adsorption of a limited amount of photoactive dye and thus leading to a poor light harvesting. Moreover, solid-state DSSCs are characterized by incomplete electrolyte filling, impeding the dye regeneration. Both limitations further lead to low photovoltaic efficiencies. Due to the surface area improvement as well as the perfect control of the pore organization and the pore size, the templating strategy was investigated to overcome light harvesting and pore filling limitations. Templated films were prepared from different structuring agents. They show an efficient electrolyte infiltration and a two times higher dye loading compared to nanoparticles layers. Corresponding photovoltaic performances in liquid-state and solid-state DSSCs have also been evaluated. While templating allows improving the liquid-state cells efficiencies, we cannot conclude for solid-state DSSCs due to device assembly issue and/or bad contacts between the electrodes and the sample holder during the I-V measurements. We hope that the achievements of this thesis brought a significant contribution to the field of DSSCs. Indeed, the templating strategy is proved to improve the liquid-sate cells efficiency. However, the assembly of solid-state devices and subsequent I-V tests have to be investigated further. Besides, new pathways are envisaged for interesting future work in both fundamental and applied research fields, such as the synthesis of templated films with hierarchical porosity or scale-up and industrialization of the templated devices. [less ▲]

To our knowledge, the stability results reported in the literature only concern cells made from classical doctor-bladed or screen-printed nanoparticles films. This study focuses on the comparison of the ... [more ▼]

To our knowledge, the stability results reported in the literature only concern cells made from classical doctor-bladed or screen-printed nanoparticles films. This study focuses on the comparison of the long-term stability of these cells with DSSCs working with templated mesoporous films. Indeed, the increased surface area of templated films could lead to a faster degradation of the resulting cells. In accordance with IEC:1646:1996 standard tests, light soaking test at 45°C has been applied to determine the cells stability under prolonged illumination. Moreover, thermal stress in the dark has been applied. Unfortunately, due to the sealing material heat resistance, thermal stress test was only performed at 45°C. [less ▲]

Hierarchical porous structures, with different pore sizes, constitute an important field of research for many applications. However, increasing the pore size results in the decrease of specific surface ... [more ▼]

Hierarchical porous structures, with different pore sizes, constitute an important field of research for many applications. However, increasing the pore size results in the decrease of specific surface. There is a need to quantify and predict the resulting porosity and specific surface. We have prepared hierarchical porous TiO2 thin films either by surfactant templating (soft) or dual surfactant/microspheres templating (soft/hard). They all show narrow, bimodal distribution of pores. Soft templating route leads to very thin films showing high specific surface and bimodal porosity with diameters of 10 nm and 54 nm. Dual templating route combines a Pluronic surfactant-based precursor solution with polystyrene (PS) microspheres (diam. 250 nm) in a one-pot simple process. This gives thicker films with a bimodal distribution of pores (8 nm and 165-200 nm). The dye loading of hierarchical films is compared to pure Pluronic-templated TiO2 films and shows a relative decrease of 29% for Single Templating (ST) and 43% for Dual Templating (DT-250). Finally, a geometrical model is proposed and validated for each system, based on the agreement between calculated specific surfaces and experimental dye loading with N719 dye. [less ▲]

Although Platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative ... [more ▼]

Although Platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative cheaper catalyst materials did not yet yield to equivalent efficiencies. In this work, we tried to understand how to reduce the amount of deposited Pt-material and simultaneously to deliver higher DSC performances. We systematically compared the properties of Pt-counter electrodes prepared by simple solution deposition methods such as spray-coating, dip-coating, brushing with reference to the Pt-electrodes prepared by sputtering onto fluorine doped-tin oxides (FTOs). The morphological and structural characterizations of the deposited Pt-layers were performed by atomic force microscopy (AFM) and scanning electron microscope (SEM). The composition of Pt-material was quantified by using SEM electron dispersive x-ray (EDX) mapping measurements are further compared with optical transmission measurements. Also contact angle and sheet resistance measurements were performed. By taking Pt-layers composition, morphology and structural factors into account 9.16% efficient N3 dye based DSCs were assembled. The DSCs were subjected to various opto-electrical characterization techniques like current-voltage (I-V), external quantum efficiency (EQE), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and transient photo voltage (TPV) measurements. The obtained experimental data suggest that the Pt counter electrodes prepared by solution deposition methods can also reach to high DSC device performances with a consumption of very less amount of Pt material compared with sputtered Pt-layers. This process also proves that higher DSC performances are not limited to the usage of sputtered Pt-layer as counter electrode. [less ▲]

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes ... [more ▼]

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes with a thickness of 10-15 µm. Templated-assisted dip-coating techniques are used to obtain thin films with ordered porosity. However, monolayer films prepared by dip-coating from a solution suffer from a low quantity of active material with a limited surface area, leading to poor photovoltaic performances. Therefore a multilayer deposition process is needed to increase the film thickness along with surface area. Multilayer dip-coating procedures have already been reported but are usually characterized by a lack of linearity in the evolution of parameters (roughness, surface area, PV performances) as the number of layer increases. In this study, we investigate a dip-coating-based multilayer deposition technique delaying these limitations. First, the influence of the template on the film organization and porosity is studied in terms of long-range order, percentage of porosity, pore size, surface area and pores connectivity. Different techniques such as transmission electron microscopy (TEM), atmospheric poroellipsometry (AEP) and UV-visible absorption spectroscopy (UV-vis.) have been used to describe the microstructural features of the films. The film exhibiting the highest dye loading was selected and its thickness gradually increased up to 4 µm. Finally, the photovoltaic performances of the thick films (1 to 4 µm) have been evaluated in combination with the N719 dye and a liquid electrolyte and show excellent efficiency (6.1%) when compared to values reported in the literature. Such mesostructured films were compared in terms of photovoltaic performance with TiO2 nanoparticles films, generally used in DSSC. Films were further evaluated by Rutherford Backscattering Spectrometry (RBS) as high performance photoelectrode in solid-state DSSCs, in combination with Z907 dye and Spiro-OMeTAD as solid electrolyte. [less ▲]

The additional energy spread due to sample porosity was implemented in the SIMNRA simulation code, version 6.60 and higher. Deviations of the path length and energy loss distributions from the ones ... [more ▼]

The additional energy spread due to sample porosity was implemented in the SIMNRA simulation code, version 6.60 and higher. Deviations of the path length and energy loss distributions from the ones expected from a Poisson distribution of the number of traversed pores are taken into account. These deviations are due to the interaction of pores at higher pore concentrations by overlap or blocking. The skewnesses of the energy distributions are approximated by two-piece normal distributions with identical first three moments. Propagation of porosity-induced energy spread in thick layers is taken into account. Calculated results are compared to experimental data obtained with thin TiO2 mesoporous films measured by Rutherford backscattering (RBS),transmission electron microscopy (TEM), and atmospheric poroellipsometry. [less ▲]

This study quantifies the highest perturbation encountered by the first layer of a TiO2 12 layers-mesoporous coating, which is submitted to a multistep calcination process. Besides, we propose an ... [more ▼]

This study quantifies the highest perturbation encountered by the first layer of a TiO2 12 layers-mesoporous coating, which is submitted to a multistep calcination process. Besides, we propose an alternative thermal treatment in order to limit the degradation induced by repeated calcinations. This paper reports and compares the modifications in film thickness, surface area, anatase crystallite size and global crystallinity of films obtained from different thermal treatments. It defines the maximum crystal size compatible with the preservation of the mesoarchitecture initially induced by templating. Differences in microporosity and rate of crystallization are also discussed. [less ▲]